Scandium(III) Catalysis of Transimination Reactions. Independent and Constitutionally Coupled Reversible Processes
作者:Nicolas Giuseppone、Jean-Louis Schmitt、Evan Schwartz、Jean-Marie Lehn
DOI:10.1021/ja042469q
日期:2005.4.1
self-sufficient transimination reaction between various types of C=N bonds in organic solvents, with turnover frequencies up to 3600 h(-)(1) and rate accelerations up to 6 x 10(5). The mechanism of the crossover reaction in mixtures of amines and imines is studied, comparing parallel individual reactions with coupled equilibria. The intrinsic kinetic parameters for isolated reactions cannot simply be added
Sc(OTf)(3) 有效地催化有机溶剂中各种类型的 C=N 键之间的自给转移反应,转换频率高达 3600 h(-)(1),速率加速高达 6 x 10(5 )。研究了胺和亚胺混合物中交叉反应的机理,比较了平行的单独反应与耦合平衡。当几种组分混合时,孤立反应的内在动力学参数不能简单地相加,并且系统的行为与构成竞争反应网络核心的独特介质的存在一致。在混合系统中,每个胺或亚胺根据它们对催化剂金属离子中心的结合亲和力竞争同一个中心枢纽。更普遍,